Mccoy m. gibson jr.	c. marshall dann



United. States Patent 1 Claim. (Cl. 260-348) This application is adivision of our copending application, Serial No. 144,575, filed October12, 1961, now Patent No. 3,065,209.

This invention relates to -1,2,5,6-diepoxycyclooctane, and tocompositions and resinous products obtained therefrom. The diepoxide ofthis invention is of particular interest in the plastics and resinsindustry and is particularly adapted for use in the preparation ofresinous products by reaction with difunctional organic chemicalcompounds such as diarnines, dialdehydes, dicarboxylic acids, diols andthe like. The resinous products thus produced can then be formed intouseful articles or employed in electrical applications as pottingcompositions. Furthermore, the diepoxides of this invention will reactwith adipic acid to form flexible, thermoplastic resins. Consequently,this diepoxide, in admixture with adipic acid, provides compositionswhich are particularly desirable for use in coating applications whereinflexible, thermoplastic surface coatings are desired. In .addition,1,2,5,6diepoxycyclooctane is also useful as a stabilizer for vinylchloride resins.

The 1,2,5,6-diepoxycyclooctane of this invention can be representedgraphically by the following general formula:

GET-CH2 The preparation of the diepoxide is carried out by reacting1,5-cyclooctadiene and at least 2 moles of peracetic acid, per mole of1,5-cyclooctadiene. The reaction of 1,5-cyclooctadiene and peraceticacid is preferably carried out by the addition of an excess amount ofperacetic acid to the 1,5-cyclooctadiene at temperatures in the range offrom 25 C. to about 150 C. and preferably in the range of from 0 C. to45 C. The reaction is exothermic and external cooling can be applied, ifdesired, to maintain the desired temperature and to assure a reasonablereaction rate. The reaction is allowed to proceed until an analysis of asample of the reaction mixture indicates that the theoretical amount ofperacetic acid has been consumed. The product is recovered from thereaction mixture by separation of the unreacted peracetic acid under anysuitable conditions which will not destroy the epoxide groups. Preferredmethods for recovering 1,2,5,6-diepoxycyclooctane from the reactionmixture include extraction, continuous distillation and distillationunder reduced pressures.

In formulating compositions of 1,2,5,6-diepoxycyclooctane with adipicacid sufficient acid is admixed with the 1,2,5,6-diepoxycyclooctane Soas to provide a composition containing from about 0.5 to about 1.2carboxyl groups per epoxy group. Heating the compositions, soformulated, at elevated temperatures, generally on the order of about120 C. to about 160 C. for a period of time of about 5 to about hourswill result in the production of a resinous product which is flexibleand thermoplastic. The exact hea-ting cycle will depend, of course,

"ice

on the particular composition being heated. The followng examplesillustrate the present invention and are not intended to limit the scopethereof in any manner.

EXAMPLE 1 Preparation of 1,2,5,6-diepoxycycl00ctane 1,5-cyclooctadiene(25 grams, 0.231 mole) was placed in a flask fitted with a stirrer andexternal cooling, and 188 grams of a 23.4% solution of peracetic acid inethyl acetate (44 grams, 0.578 mole of peracetic acid) was addeddropwise over a period of twenty-five minutes. During the addition andfor two hours thereafter, the reaction solution was maintained at atemperature of 35 C. At the end of this period, an analysis forperacetic acid indicated that 97.8% of the theoretical amount ofperacetic acid had been consumed.

The reaction solution was then added dropwise to a still kettlecontaining ethylbenzene fluxing at 25 mm. pressure. During the addition,there was distilled at the head enough material so that a headtempertaure of 30 C. to 32 C. was maintained. After addition, alowboiling material was distilled up t the boiling point of pureethylbenzeue. There remained 72 grams of residue product which analyzed0.14% as acetic acid. The residue product was fractionated through aten-inch column packed with glass helixes, and there was obtained 27grams of 1,2,5,-diepoxycyclooctane which represented an 84.0% yield. Theproduct, 1,2,5,6-diepoxycyclooctane was characterized and had thefollowing physical properties:

Analysis-Calculated for C H O Theoretical Found 0, percent 68. 54 68. 40H, percent 8.63 8.77

EXAMPLE 2 Control 1, Composigram tion A,

gram

1,2,4,5-diepoxycyc1ohexane 0. 6 1,2,5,6-diepoxyeyc 0.7 Adipie acid 0.370.37 Carboxyl group per epoxy group 0.6 to l 0 6 to 1 Each compositionwas subjected to the following heating cycle: seven hours at atemperature of C., and then six hours at a temperature of C.

At the end of the heating cycle, the product obtained from Control 1 wasyellow in color and was a tough, infusible thermoset resin which had aBarcol Hardness of 57, determined using a Barcol Impres-sor GYZJ 934-1.

At the end of the same heating cycle, the product ob tained fromComposition A was a soft, flexible, thermoplastic resin which melted,when heated to a temperature of 160 C.

What is claimed is:

The diepoxide, 1,2,5,6-diepoxycyclooctane of the formula:

OTHER REFERENCES 'CHr-CHz 5 Bedos, Comptes Rendus., vol.. 195 pp.802-804 (1932). Ed Carroll, Plastics Technology, vol. 7, 1961, pp.52-54. Fieser & Fieser, Organic Chemistry (3rd ed.), 1956, I pp. 46 and47.

OE g Foster et al.: J.A.C.S., vol. 70, No. 7, pp. 2303- CHzCHz I I 1Richter (I), The Chemistry of the Carbon Compounds 1 (A1icyc1ic), vol.2, page 1 (3rd ed.), 1939. References by the Exammer Richter, TheChemistry of the Carbon Compounds,

UNITED STATES PATENTS v01. 4, pp. 4 and 5 (1947). 5 1 0 1 1951 Craig2'5'0 343 5 Lee et 81.! EPOXY Resins, MCGIaW-HiH BQOR CO- w2 739 1 1 3Cal-15011 2 343 (P g 218-19 and 225 felled 2,745,847 5/1956 Philli eta1. 260-348 et 1 A. Primary Exammer. 22,786,067 3/1957 Fristick et a1.260-348 IRVING MARCUS, Examiner.

4 FOREIGN PATENTS "520,163 "4/1940 Great Britain.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3244,732 Dated April 5, 1966 Inven r(s) F;C. Frostick, Jr. et a1 It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

In Column 1, Line 13, after "Patent No. 3,065,209"

insert --which in turn is a continuation-in-part of copendingapplication serial number 527,424, filed August 9, 1955, now abandoned."

Signed and sealed this 8th day of October 1974.

(SEAL) Attest:

MCCOY M. GIBSON JR. Attesting Officer C. MARSHALL DANN Commissioner ofPatents FORM PO-105O (10-69) uscoMM-oc 60376-0 09 i l-LS. GOVIIIIIUIYPIIIITING OI'FICI "II 0-JIO-J3L

